Hydrogenation furnace



silepm 1'-, w23; Mamas T. NUSD'GLEK JRI HYDRoGENAT-ION -FRNAQE Filedoct. 5, i918 2 sheets-sneeil 75 v.

@Sm '1112;1'923, ummm v T. MID'GLEWJR l HYDRO'GENATI ON FURNACE :Filedoct. 5, 1918V 2 sheets-sheew lPaterated Sept. lill, 1923..

UNET@ `TAS ATN'T @PECO TOMAS MIDGLEY, JR., OF DAYTON', OHIO, ASSIGNOR,BY IJImNE ASSIGNMENTS, TO

-GENE MOTO RESEARCH CORPORATION, 01"* DAYTON, OHIO, A CORPORATION OFDWE.

I HYDROGENATION FURNACE.

, new and useful Improvements in Hydrogenation Furnaces, of which thefollowing is a full, clear, and exact description.

This invention relates to hydrogenation and more particularly to amethod of hydrogenation adapted for the preparation of fuels fromunsaturated hydrocarbons and to an apparatus for carrying that methodinto edect. .y Y The principal object of the invention is to provide animproved method of hydrogenation which is especially efficient in thatthe materials entering into the reaction chamber are fed into theapparatus'continuously under pressure so that continuous operation ise'ected, and to provide improved apparatus for carrying that method intoeffect.

Other objects and advantages of the present invention will be apparentfrom a description thereof set out below.

This method of hydrogenation and the apparatus for carrying it intoeffect have been especially designed for hydrogenating benzene toproduce cyclohexane, or mixtures of benzene .and cyclohexane containingthese two 'constituents in any desired proportions. llt is not, however,limited to the hydrogenation of benzene inasmuch as it is adapted forhydrogenation generally.

In hydrogenation in the gaseous phase, as heretofore carried on, the.reaction has been intermittent. rThat is a mixture of hydrogen and thevaporized material to be hydrogenated has been forced into the reactionchamber and over the catalytic material under the desired pressure, thehydrogen and vaporized material .associated therewith being handled insmall charges, each charge being fed to the reaction chamber andcompletely acted upon before -the next charge is introduced. Tn mymethod the mixture of hydrogen and the vaporizd material tobehydrogenated is fed into the reaction chamber and over the catalyticvmaterial therein continuously, the desired -pressure within thereaction chamber being maintained at all times by feeding the mixturevantageous and that much better results will be obtained than with theintermittent methods heretofore practiced. For carrying this method intoe'ect I make use of the apparatus illustrated in the accompanyingdrawing in which- Fig. 1 represents a preferred embodiment of a form ofapparatus used by me; and

Fig. 2 represents a modified form of reaction chamber, adopted as asubstitute for the reaction chamber -illustrated in Fig. 1.

Tn the drawing, like characters of reference designate like partsthroughout the several views thereof.

Referring to Fig. 1, 10 is a reaction chamber having the lower endpermanently closed and the upper end closed by means of a removablecover 11 held tightly in place by any desired means. Leading into thechamber 10 is an inlet pipe 12 adapted to supply thereto a mixture ofhydrogen and the vaporized material to be hydrogenated. The inlet pipe12 is connected to a chamber 13 adapted to receive vaporized benzene, orother vaporized material to be hydrogenated, and hydrogen. ber 13 is asupply pipe lthrough which the material to be hydrogenated is lforced ataieiy desired pressure by means of the pump l Cooperating with the pipe15, adjacent the chamber 13, is a gas heater 14 adapted to heat asection of the pipe to vaporize any benzene or other material passingtherethrough. This heater and the pipe associated therewith are inclosedin a Inutile 17, shown as partly broken away, the arrangement being suchthat any desired temperature may be used in carrying on thevaporization. By proper regulation of the pump the pressure at which thevaporized material is forced into the chamber 13 may be maintainedconstant. Any other desired means may be -used for vaporizing thebenzene or other material to be hydrogenated. For example this materialmay be passed through pipes heated by a lead bath, or it may be passedover coils heated by steam. Tt is merely necessary that the material bein vaporous form when passing through the reaction chamber. Associatedwith the pump 16 is a pressure regulated throttle valve 18, responsiveto variations of pressure within the pipe 15 and adapted to vary thesupply of steam, or other operating fluid, to the Leading into thechampump 16 to ymaintain a 'continuous pressure within the pipe .15, andthus to maintain continuous the pressure under which the material to be'hydrogenated is sprayed into the chamber 13. Leading into the chamber13 is a second supply pipe 20 through which hydrogen is admittedthereto. This pipe is connected to a storage tank 21 which is keptsupplied with hydrogen under any desired pressure by means of a pump 22.Cooperating with the pump 2,2ffis' a pressure operated throttle valve 23responsive to variations in pressure within the delivery pipe 20 andadapted .to vary the operation ofthe pump 22 to maintain constant, andat any desired pressure, the pressure within the storage chamber 2.1.From the vstructure thus described it is obvious that a mixture ofhydrogen and vaporized material to bev hydrogenated is fed continuouslyunder any desired pressure 4from the chamber 13 through the pipe 12 intothe interior of the hydrogenation furnace or reaction chamber 10.

Carried by the inner wallY of the chamber 10 is a shelf or ridge 25adapted to support a cartridge 26, the cartridge having a flange aroundthe upper end thereof cooperating with said shelf. Between this flangeand the shelf is a gasket 27, of any desired material, adapted toprevent the passage of any of the hydrogen or vaporized material betweenthe walls of the reaction chamber and the cartridge so that all of thehydrogen and vaporized material will pass through the catalyticmaterial. The cartridge 26 consists of a seamless tube adaptedy tocontain catalytic material 28. In the hydrogenation of benzene I havefound a catalyst of nickel i -out requirin chamber, an withoutinterfering hardly at oxide to give very satisfactory results, but ofcourse other catalysts may be usedias conditions may demand. For holdingthe catalytic material within the cartridge it is closed by a perviousplate 29 held in place by an internal flange around the lower endthereof. By providing a catalyst container of this sort, capable lofready removal through the upper end of the reaction chamber, thechanging of catalytic material is greatly facilitated and, what has beenhere` tofore a difiicult and tedious job requiring a lengthy shut-downin operation, is made considerably easier, the entire change, whichconsists in removing the cartridge containing the spent catalyst andsubstituting therefor a cartridge containing a fresh catalyst, beingaccomplished in a few minutes withcooling 0H of the reaction all withoperation.

Surrounding the reaction chamber 10 are "a number of resistance orheating vcoils 30 'each coil being connected by means of'suitableconductors 31 with any desired source of electrical current, (notshown). Coop- Memos erati with each heating coil 30 is a switch 32 aapted to control iow of current through such coil, to thus control theheating effect of the coil. The turns of each coil are insulated fromeach other, and the coils themselves are insulated from each other, bymeans of any desired insulating material. As shown, the wiresconstituting these coils are embedded in an insulating layer 33 ofalundum. The specific type of insulating material, however, isimmaterial, other materials being capable of functioning satisfactorily.

An additional control of the temperature within` the reaction chambermaybe efected by a control of the. radiation of heat therefrom. For thispurpose the chamber carrying the heating coils is covered with heatinsulating material. Any desired type of heatinsulating material may beused but in my work I have found such material as asbestos'or magnesiato belvery satisfactory. As-shown in Fig. 1 of the drawing the heatingcoils cover that part of the reaction chamber containing the catalyticmaterial, and the heat insulating material is preferably made up in theform of semi-cylindri-l within the chamber 10. Any number of heatingcoils and insulating sections other than the number shown may be used ifdesired, a greater number permitting` a nicer control, and a smallernumber less control of heat conditions.

Hydrogenation always takes place most favorably, for any particularmaterial, within a certain definite temperature range; In order thatthis'temperature within the reaction chamber may be attained, duringinitial operation of the apparatus, it is necessary to completely closelthe heat .insulating doors 35 and to pass an electric current through'each of the heating coils 30. When the desired temperature has beenattained andthe hydro 'enation reaction is proceedin satisfactorlly theheat of reaction will be considerable, and generally, as in thehydrogenation of benzene, more than suilicient to maintain thereaction.' If the heat insulating doors 35 are maintained in closedposition temperatures willbe reached which will themes reaction becauseof dehydrogenation. After hydrogenation is fairly under way thereforeheat from the coils vis generally no longer necessary and consequentlythe current Howing therethrough may be interrupted. In addition itfrequently becomes necessary to open theheat insulating doors in orderto permit the dissipation into the atmosphere of some of the excess heatgenerated by the reaction. As stated above this apparatus was devisedparticularly for the hydrogenation of benzene, to secure either4cyclohexane or a mixture of benzene and cyclohexane in .any desiredproportions. ln the hydrogenation of benzene l have found that pressuresof approximately 300 pounds per square inch and a temperature .ofsubstantially 300 centigrade maintained within the reaction chamber givevery satisfactory results. Any substantial variation above or. belowthis temperature results in a rloss of eiciency.

F or determining the-temperature within the reaction chamber ll make useof thermocouples 40C, which may be of any desired materials, a pluralityof thermo-couples being used, not less than one to each heating coilbeing desirable, which are embedded directly in the wall of the reactionchamber. Each of these thermo-couples is connected with a Aswitch 41 allof the switches being connected toa potentiometer; As shown in thedrawing, the poles of the switches are connected direct to thepotentiometer in parallel, a separate switch being provided for eachthermo-couple. ln order to determine the temperature of that part of thereaction .chamber cooperating with the particular thermo-couple it ismerely necessary 'to close the switch connecting the said thermo-couplewith the potentiometer. rlhe potentiometer may, if desired, becalibrated to read temperatures direct, but if not so calibrated it isquite easy to determine actual temperatures from the potentiometerreadings. By means of this temperature indicating device it is a vesimple matter to determine the heat con itions Within any particularpart of the reaction chamber and, by

means of the heating coils and the heat insulating doors, to maintainthe desired heat conditions Within such reaction. chamber.

Leading oli' from the bottom of the reaction chamber 1() is an outletpipe 50 which leads into a condenser 51 in which any vaporous materialpassing out of the reaction chamber will be condensed and will drain oilthrough the pipe 52 into the collecting trap 53. Leading od from thetrap 53 is a pipe 54, How through which is controlled by means of thefloat operated `valve 55. When the level of the liquid within the trap53 rises to a predetermined height the doat operated valve 55 will'beopened to allow the escape of liquid therefrom until said valve is againseated. rlhis pipe 5e leads drometer 61. lf it is desired to determinethe character of the fluid resulting from the hydrogenation within thechamber 10 it is merely necessary to close the valve 57 and open thevalve 59 whereupon fluid flowing from the trap 53 will pass into thesampling tubel 60 where its specific gravity may be read directly bymeans of the hydrometer 61. to form a mixture of cyclohexane andbenzine, such a mixture for instance as is described in my copendingapplication Serial No. 256,874 filed Oct. il, 1918,it isn quite easy todetermine by means of the hydrometer whether'the mixture coming ofi fromthe reaction chamber is of the proper consistency and if not to alteroperating conditions Vto secure the desired. mixture. With thisapparatus benzene may-be hydrogenated completelyV into cyclohexane, orinto Where benzene is being hydrogenated y any desired proportion ofbenzene and cycloy hexane. genation it is merely necessary Yto vary therate at which the benzene is fed to the reaction chamber, the faster itis fed thereinto the less time it is subjected 'to hydrogen'atingconditions and the smaller the percentage which is changed. Obviously byfeeding the benzene slower or faster the time of reaction may be variedto 'secure any desired degree o-f hydrogenation, and the sampling tubeand hydrometer permit of determining directly what the degree ofhydrogenation is so that the rate of feeding may be intelligentlycontrolled. 0f course this is true in the hydrogenation of materialsother than benzene.

Leading off from the condenser 51 is a recirculating pipe 70, the otherend of which opens into the upper end of the reaction chamber 10. Anyhydrogen that may pass on' from the reaction chamber into the condenser51 will be returned through this recirculating pipe to the upper endofthe reaction chamber where it will again take part in the reaction goingon therein. Surrounding the recirculating pipe 70, adjacent the placewhere it opens into the upper end of thechamber 10, is a condenserconsisting of a chamber 71 having inlet and outlet 'pipes 72 and 73through which water or other cooling fluid is supplied thereto. vThatportion of the recirculating pipe cooperating with this condenser is soinclined that anycon- To control the degree of hydro- 'i llt) nac

' material 85. Carried by the inner wal action chamber through therecirculating P1P@- In Fig. 2 of the drawing I have illustrated areaction chamber of a modified form. As illustrated the reaction takesplace in a chamber 80 which is open at both ends, the upper end beingclosed by means of a removable cap 81 through which opens an inlet pipe82, corresponding to the inlet pipe 12 of Fig. 1 and adapted tocooperate with just such a vaporizing chamber and supplying means asillustrated in Fig. 1. lso opening into the 'reaction chamber throughthe cap 82 is the upper end of a recrculating pipe 83, the functions o fwhich are similar to those described in connection with therecirculating pipe shown in Fig. 1. The lower end of the reactionchamber is closed by means of a removable cap 87 having upstanding lu s86 thereon adapted to support a perforate plate 84 which in turnsupports a metallic cartridge 88 containing catalyti -o the reactionchamber is a shel'rorridge 89, and located between the lower surface ofthe shelf or ridge and the upper part of the cartridge 88 is a packing90. In assembling,

the cartridge 88 is inserted into the reactionchamber wlth the upper endof the frame work abutting the packing 90 which is in' turn in contactwith the ridge 89. The per- Jorated plate 84 is now inserted and the cap87 placed in p'osition with the lugs 86 thereof in contact with the saidplate. As the bolts 91 are tightened the cap 87 is forced upwardlycarrying the plate 84 with it. The cartridge 88 is thus forced againstthe packing 90 compressing lsuch packing against the cooperating ridge89 to form a tight joint adapted to prevent the passage of any of thehydro 4en or vaporized material between the wal of'the reaction chamberand the cartridge 88, so that all of the hydrogen and vaporized materialwill pass through the catalytic material.

Leading off from the bottom of the reaction chamber is an outlet pipe100 which leads into a condenser 101 having an outlet pipe 102 leadingtherefrom into a trap and collecting mechanism similar to that disclosedin Fig. 1.

Surrounding the reaction chamber is a K heating coil 95. As illustratedthis heating coil consists of a pipe through which steam vor otherheating material is adapted to be circulated to secure the desiredtemperature within the chamber. It is obvious that this type ofapparatus does not lend itself to such a nice and accurate control ofheat conditions within the reaction chamber as does the type ofapparatus illustrated in Fig. 1.

- This type of apparatus is, however, eiective and quite satisfactoryunder general operating conditions.

From the above description the operation menace the cartridge andcatalytic material coni' tained therein. The reaction chamber, includingthe catalytic material, is maintained at the temperature necessary forsecuring the most eilicient reaction by means of the heating coils andcooperating heat insulating doors. As stated above the degree ofhydrogenation is varied by varying the period during which the materialto be hydrogenated is exposed to the catalytic material in the presenceof hydrogen. The vaporized hydrogenated material, along with anyuncombined hydrogen, passes into the condenser 51 where the vaporizedmaterial condenses and flows into the trap 53 and from there to thecollecting tank 56. The uncombined hydro en returns through therecirculating pipe 0 to the top of theireaction chamber whence it again.passes The mixed hydrogen and vapor# th'rough the catalytic material totake part.-A in the reaction. The mode of operation 01?1'00 the modifiedform of reaction chamber shown in Fig. 2 is practically the same.

It is obvious from the above description that I have invented aneiicient method of hydrogenation, and one which lends itself to greateconomy of operation. It is further obvious that I have devisedapparatus for carrying that method of hydrogenation into effect which isnot only very eiiicient and eective but is also comparatively simple inconstruction and lends itself to easy operation.

While the method herein described, and the forms of apparatus forcarrying that method into eect, constitute preferred em bodiments of theinvention, it is to be understood that the invention is not limited tothis precise method and these forms of apparatus, and that changes maybe made in either without departing from the scope of the inventionwhich is defined in the appended claims,

What I claim is as follows:

1. The method of hydrogenati'ng benzene which consists in introducinghydrogen and Vbenzene vapor into the presence of catalytic menace r tionchamber 4adapted to contain calytic material; a heating jacketassociated therewith, said jacket comprising a plurality of unitscapable of separate operation to heat the whole chamber or any desiredpart thereof.

3. ln a hydrogenation apparatus, a reaction chamber adapted to containcatalytic material; a heating jacket associated there with and soarranged as to heat the whole chamber or' an part thereof; and meansassociated with the chamber and the jacket for varyin the intensityofthe heating eect of the jac et upon the chamber.

a. ln a hydrogenation apparatus, a reaction chamber adapted to containcatalytic material; a heati jacket therefor; and means associated wlththe chamber and the jacket for varying the intensity of the heatlng eectof the jacket upon the chamber, said means consisting of a plurality ofunits, arranged to 'control the radiation of heat from the jacket awayfrom the chamber.

5. llna hydrogenation apparatus, a reac= tion chamber adapted, tocontain catalytic material; heating means therefor, said meanscomprising a plurality of units capable of simultaneous or separateoperation to heatvthe whole chamber or any desired part thereof; andmeans comprising a pluralit of units adapted to coact with the heatingunits to control the amount of heat lost b radiation away from thechamber.

6.. n a hydro enation apparatus, a reaction chamberv a apted to containcatalytic material; heating means associated therewith adapted to heatthe whole chamber or any part thereof; heatinsulating means associatedwith the chamber and heating means, adapted to heat insulate the wholechamber or any Ipart thereof; and means for accurately determining thetemperature of any part of the chamber.

7. lin a hydrogenation apparatus, a reaction chamber adapted towithstand high internal pressures,an inlet thereinto, and outlettherefrom; a condenser connected to said outlet; and a recirculatingpipe leading directly vfrom said condenser to the upper end of saidchamber.

8. lin a hydrogenation apparatus, a reaction chamber, an inletthereinto, an outlet therefrom; a condenser connected to said outlet; arecirculating pipe leading from said .condenser to the upper end of saidchamber;

and a second condenser surrounding the upper end of said recirculatingpipe.

. 9. lin a hydrogenation apparatus comprising a reaction chamber adaptedto withstand high internal pressures, having an inlet and.

an outlet; a recirculatin pipe directly connecting the outlet of saichamber to the upper end thereof.

10. ln a hydrogenation apparatus comprising a reaction chamber, havingan inlet .and an outlet; a recirculating pipe connecting the outlet ofsaid chamber to the upper end thereof; and a condenser surrounding theupper end of said recirculating pipe, said pipe and condenser being soarranged that any condensate therein will flow into the chamber.

ln testimony. whereof l alix my signature.

THUMAS MlDGLEY, Jn. Witnesses C. Nar-ZEN, M. E. GREENE.

